Process of enhancing the flow of oils through pipe lines



I Patented Apr. 15, 1930- annular a. scan:

1 AN, CHICAGO, ILLINOIS, ASSIGNOB '10 CATALYTIC CHEMICAL com, 0! DENVER, COLORADO. A CORPORATION OF COLORADO race or R o Drawing.

' The present invention relates to a pr'ocess of treating mineral oils and petroleum prodacts and ydrocarbon products that are to be pumped through pipe lines.

'5 My process is particularly designed for the treatment of petroleum products that are heavy and viscous due to the presence therein of waxes and pitches. The process is also applicable to the treatment of oils containing water in the form of an emulsion.

An object of my invention is to lower the cold-test of mineral oils, petroleum products and similar hydrocarbon products and to lower materially the viscosity of such products tending to reduce the flow through the pipe farm is very reat, it is custom aryto have pumping and eatinglstations at intermedi-.

line, as well as to increase the cost of pum ing. While I am aware that natural petro eum oils which are too viscousto be pumped or otherwise handled, and by reason of this have not been used as combustibles, for instance, in oil-fed furnaces in which the fuel oil is pumped to the burners and atomized, have been treated or rocessed by the simple addition of naphthalene thereto without any further chemlcal or heat treatment in order to transform the oil'into a free flowing fluid or to make it a more mobile liquidnat ordinary tem ratures so that itcan be easily pumped, am not aware that it has ever been proposed to treat heavy, viscous oil and oil roducts b 'a composition of materials as wil be descri d more fully below.

In connection with'pipe lines, the crude petroleum may be pumped from the wells to the tank'farms or tank farms to the stills. Wherethe distance from the-well to the tank ate points as the oil as a tendency tochill and its viscosity increased, causing a deposit of arafline and other waxes and various products in the pipe lines so that, for example, a six inch pipe hue might be so obstructed applied in the well or at various alumina (inclu CING THE FLOW 0F OILS THROUGH PIPE LINES- Appllcatlon filed February 16, 1937. Serial No. 188,820.

that it was only equivalent to a two inch pipe. In this instance 1t is necessar' to clean the pipe lines, and in so far as I ow, this has never been proposed in the manner in which I have proposed to do it; By the employment of my recess and materials used in carmg out t e process, not only is the pi e l1ne cleaned, but by the continued use of t e materials the pipe line is maintained clean and unobstructed'so that there is an immediate saving in pumping and heating expense, and initial equipment is reduced in cost as smaller size pipe lmes may be em loyed.

My treatments or processes may he employed at other steps or points in the flow of the materials between the wells and the market, and has been, for example, founddesir able and of value in treating cracker stock either as it comes from the crude stills and prior to entering the cracker, or during the cracking process, as for example, after it has has been subjected to heat in the furnaceor heating coils and prior to its admission to the reaction chamber or while in the same or in similar or other apparatus employed in cracking processes. In the treatment of pi e lines to clean them or to keep them' clean, apply my materials or mixtures to the crude stock as it comes from the well, although the same may be oints in its flow, as will be hereinafter re erred to. For this treatment, I prefer to use a combination of materials that will break up the carbon clusters, waxes, binders, fats, etc., so that the etroleum remains more fluid and does not ave a tendency to clog the lines.

'I have found a very satisfactory mixture to consist of flake na hthalene, anthracene, a

combination of alka i which I prefer to make up with caustic soda, sodium phosphate, and ammoriiumcarbonate, together with granulated su ar, oil of mirbane, a phosphate rock or pow or or the equivalent, and a limited amount of sulphuric acid. For the phosphate rock, I have secured very satisfactory results using aFlorida phosphate rock or powder analyzing approximately as follows: Carbon dfixide, silica, phosphorous pentoxide, lime,

ing stress 9f ferr c oxide find that slight variations in the analysis of ter is added to the other ingredients.

, fluidity of the oil, to lower its cold test and to cause the liberation and separation of any.

the rocks do not affect the treatments to any extent. As an illustration, I have secured satisfactory results by the use of 133 lbs. flake naphthalene, 21 lbs. anthracene, 56 lbs. caustic soda, 10 lbs. sodium phosphate, 10 lbs.

ammonium carbonate, 20 lbs. granulated sugar, 1 lb. oil of mirbane, lb. sulphuric acid, 3 lbs. phosphate rock, and 2 lbs. of sodium hydroxide. In mixing these, I take first the caustic soda, sodium phosphate and ammonium carbonate, and mix the same with approximately an equal amount of naphthalene, and grind the same thirty minutes in a ball mill, and then add the balance of naphthalene and the proper amounts of anthracene, sodium hydroxide,oil of mirbane and phosphate rock, grinding the desired time, generally a few' minutes, say three to five minutes, and then add the granulated sugar and grind that for several minutes. The material is then dumped and packed in airtight metal drums for use. i

When used, it is applied to the crude oil in a proportion of about 1 lb. to every 30 bbls. oil, the proportions dependin on the particular oil to be treated, which is readily determined b testing. Where tank stock or residuum is treated, I treat in the proportion generally of 1 lb. to 15 bbls. of petroleum, and in instances where there is a very heavy residuum substantially 1- lb. to 8 bbls., it being understood that these proportions may be varied within considerable ranges, this, as before mentioned, being determined by test.

The lb, sulfuric acid mentioned above in connection with formula is employed to treat the 21 lbs. of anthracene before the i aif e aci-d appears to activate the anthracene or to remove therefrom certain impurities. When pure 85% anthracene is used, this sulfuric acid treatment is not necessary. The second (3 lbs.) of sodium hydroxide specified are used to treat the anthracene which has been sub-v ect'ed to the sulfuric acid treatment, as the final composition isintended to be alkaline. The oil of mirbane can be omitted in some 'nstances from the mixture without affecting its efiicacy.

In treating the crude ,oil or similar hydro carbon product, the action of theabove-mentioned mixture is to increase considerably the I moisture or water contained therein.

The reagents mentioned may be added to the crude oil at any suitable stage during their handling, either directly as they issue from the well, while in storage, or while being conveyed through pipe lines; and either prior or subsequent to any refining treatlment.

above, and which is used in carrying out mypresent invention, the naphthalene and anthracene serve to break down hydrocarbon clusters in the oils undergoing treatment, by which term I mean that the heavy waxes and other similar deposits in the oil are rendered soluble and hence the fluidity of the resultant mixture is increased. It is impossible to state exactly the chemical action due to the adding of the caustic soda, sodium phosphate or ammonium carbonate, but these apparently, when added to the etroleum from the well, produce an artificia heat by chemical action .and cooperate with the other chemicals in separating the hydrocarbon clusters, the same by chemical action inci'easi'ng'the temperature sufliciently to cause a permanent change of the cold test range of the oils or large bodies of hydrocarbons. These also Work with the granulated sugar, it having been found after much experimenting that there was achemical action creating more fluid substance. Of course, I know that in adding the 7 sugar, I have 'added a ercentage of moisture in itself, and taking: tli with thesugar, there is a atalytic action on the hydrocarbon clusters, eaking them and ma ing a more permanent fluid. Presumably the alkali addition breaks up the binders or cuts the binder the same as they would cutfats. By

gether, together wit the naphthalene, and anthracene which has a milder efi'ect on separatin the clusters, the binder is destroyed so that t e same is not formed again in the pipe lines or containers so far as the clusters in the the attack that the combination makes on the binder that holds the clusters'toe alkalies referred to parafline wax, asphalt or tar are concerned.

The parafiine wax, tar or' asphalt alone'may be cut by the caustic soda, ammonium carbonate and granulated sugar mixture, without the presence of carbon in the wax as I have successfully demonstrated this, to wit, by adding the combination to crude oil where it has the presence of a large quantity of gasoline and different groups of oils of low specific gravities. I found that there was a cutting action on the paraifine or wax combination so that they would not adhere at temperatures as low as 45 F., thereb indicating that the cold test is lowered. he phosphate rock ap ears to act as a clarifying agent, the proba ility bein that inasmuch as it is used .in ver finely divided condition, it will act as a mil scouring agent upon the walls ofthe pipe lines storage tank, none of the waxes or the like therein contained have been sub 'ected to any heat-treatment. Moreover,.in t e pipe lines,

' impurities, are in the crude oil.

- in the various processes following, or in the Various refinery treatments, the carbons may re-clusters so that breaking down of clusters in the crude oil may not be permanent or sufficient for all of the later products.

' As before mentioned, the employment of I my compounds and processes at any step improves the efliciency of succeeding treatments 'or processes and apparatus so that even though I prefer to treat the petroleum in succeeding refinery steps, the refining processes are improved by preceding treatments so that there is a general improvement at all points between the crude in the well and the-products to be marketed.

In using my composition of materials to remove paraffine from pipe lines, a very interesting experiment was made on a 6-inch pipe line 53 miles long. Examination at a number of point-s disclosed that the line was choked with paratline until it had only about two inches clear inside diameter. In making the experiment, 59,000 barrels of oil in tanks at the field end of the line were treated with the chemical-composition of "this invention. This-required 2850 pounds of the chemical, and required 72 hours of time. The oil was drawn from the big tanks through a series of 5000 and 10,000-barreltanks, where my composition was applied and the oil returned to storage tanks until ready for use. When all the oil had been treated, it was started through the line, and at the end of about 10 days all the treated oil had been pumped into it. Aclose examination was then made at numerous points all along the line, and the inside of the pipe was found to have been absolutely cleaned of all parafiine accumulation. The line has been in operation for a considerable time and has not paratfined since that time.

Having thus described my invention, it is obvious that in view of the many varied conditions under which petroleum and their products are treated and the various processes and the varied apparatus employed in refining and treating them, as-well as the varied characteristics of the petroleums and their, products, that considerable variation may be made from theabove disclosure without departing from the spirit of my invention as set forth in the appended claims, which should be construed accordingly.

I claim:

1. In a process for removing deposits from pipe lines used for conveying crude oil, the step of passing through the l1nes a compositign comprising naphthalene, anthracene, alkalies and sugar dissolved in oil that is being pumped through the lines.

2. In a process for removing deposits from pipe lines used for conveying crude oil, thestep of passing through the lines a composition comprising naphthalene, anthracene, alkalies, sugar and phosphate rock dissolved in oil that is being pumped through the lines.

3. In a process for removing deposits from n V pipe lines used for conveying crudeoil, the step of passing through the lines a composition comprising naphthalene, anthracene, sodium hydroxide, sugar and phosphate rock dissolved in oil that is being pumped through the lines.

4. In a process for removing deposits from "plpe hnesused for conveying crude 011s, the

step of passing through the lines a composition comprising naphthalene, anthracene, sodium hydroxide, sodium phosphate, sugar and phosphate rock dissolved in oil that is being pumped through the lines.

5. In a process for removing deposits from pipe lines used for conveying crude oils, the step of passing through the lines a comp0sition comprising naphthalene, anthracene, sodium hydroxide, ammonium carbonate, sodium phosphate, sugar, and phosphate rock dissolved in oil that is being pumped through the lines.

In witness whereof, I have hereunto subscribed my naine.

ALBERT H. AOKERMAN. 

